Surface-active agents



Patented Dec. 5, 1944 UNITED STATES PATENT-- OFFICE 2,364,348 SURFACE-ACTIVE AGENTS Joseph B. Dickey, Rochester, Y., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey Serial No. 403,879

No Drawing. Application July 24, 1941,

4 Claims.

wherein R is a substituent selected from the group consisting of hydrogen, alkyl, aryl, hetero- 1a, 1940, now U. s. Patent cyclic, cycloalkyl and naphthenyl groups are treated with hypophosphorous acid to give compounds having the formula:

OH OH R$ -P JJ-R 0 0H 4 I naphthenyl naphthenyl wherein R has the meaning referred to above.

If the reaction is stopped at the intermediate stage OH I x-d-r-wm.

nsphthenyl 'mixed acids can be formed by treating with a different aldehydic or ketonic compound. These mixed acids may be represented by the formula:

naphthenyl R! wherein R has the meaning referred to above, R

and R are similar to R and wherein R and R may be part of the same system of cyclic carbon atoms. Products of the type illustrated by this formula are obtained byreaction compounds of r the type illustrated by the structural formula R-F-haphthenyl with hypophosphorous acid and then with compounds illustrated by the structural formula PREPARATION OF ACIDS Intermediatesrequired for the preparation of the new phosphinicacids of ketones of my invention are described in the copending application of J. B. Dickey and J. G. McNallySer. No. 320,718, filed February '24, 1940, in U. S. Patents 1,988,021 and 1,989,325 and in Lewkowitsch,

Chem. Technology of Oils, Fats; and Waxes,

6th edition, 1, p. 146-155. By the term naphthenyl we referto radicals of the general class described in chapter 48 of The Chemistry of Petroleum Derivatives by Carleton Ellis.

,Typical examples of the preparation of this type of compound are given below:

" Example 1 3 moles of phenylnaphthenyl ketone are heated with 66 g. of hypophosphorous acid for one dayor more at a temperature of -100. ing product having the formula:

o=P-on (Biaphenylnaphthenyl hydroxy methane phosphinic acid) crystallizes out. There is also formed some Upon cool- OH LP-(on naphthenyl which is quickly oxidized to Example 1A 3 moles of xylyl naphthenyl ketone are heated with 66 g. of hypophosphorous' acid for one day or more at a temperature of 60-100. Upon cool ing a product having the formula: I

crystallizes out. li'here is also formed some nnphthenyl 2 I 2,304,848 which is quickly oxidized to (F) l (CH1): H'N OH OH @(J-naphthenyl i -OH 5 mphthenyl L.... F 2' 0 0H 0 Example 2 2.5 gram moles methylnaphthenyl ketone are h dr 45-min 11 1 nm lhd: m reacted with 66 g. of hypophosphorous acid as in y liiio fiinlc'fid) my y me we Example 1. The product has the formula: (G)

on; on 5; noo -P d-on 15 O 0 03 i HO- r'naphthenyl naphthonyl naphthenyl L 1 (Bls s1pha-nsphthenyl-alpha-hydmxy ethane phosphinlc acid) 0:] 0H

' no isdimth in n 1 11th "lh'drz 3 msmiz piosgiisih 1 One gram mole of dinaphthenyl ketone is re- Example 3A acted with 66 g. of hypophosphorous'acid as in Example 1 and the intermediate product thus formed is heated as before with two moles of.

The product has the formethylamyl ketone. mule:

(Di-naphthenyl hydroxs methanei-g)eta-hydroxy heptane phosphinlc The compounds listed below represent in gen eral the products of this invention prepared by mphthenyl (Meta-sulfo phenyl naphthenyl hydroxy znfithanwbete-hydmzy hexane phosphinlo oci nephthonyl 0H o yl-fi-sulfo-l-naphthylnaphthenylh drp methaneaydroxy-alpha-cyolopentylethanop osph caold) R (Z-isogr alp "( Y H K (Bis-naphthenyl hydroxy olohexano hydroxy methane phosp 1110 said) 3 moles of naphthenyl aldehyde, prepared by treatingnaphthenio acid chloride with hydrogen over paladiumized barium sulfate, is treated with 65 g. of hypophosphorous acid for 1 day at 109". Upon cooling 2. product having the formula OH nophthenyl+ P-O H mphthontl- -P (8-- CHI m mmyPL-w I H Bil-LU naphthenyl$-P H OH AH CH: naphthenyl-1 (5-0yclohcxyl H OH H PREPARATION OI SALTS I Example;

One mole of naphtbonyk- -otearyl 2 is treated in water with 1'mole potassium hydroxide. The product, potassium bis-naphthenyl acetoxy stearyl methane phosphonic acid salt is slightly soluble in hot water. In place of potassium I may prepare the sodium, ammonium, calcium, barium, magnesium, etc... salts. L

Example 5 One mole of is reacted with triethanolamine in the dry state or in any suitable solvent. The'salt tormed is his alpha-naphthenyl-alpha-hydroxy-ethane phosphinic acid triethanolamine salt. In place of triethanolamine 1 may use ethanolamine, diethanolamine, glycerolamine, mono-, di-, or tributylamine, cyclohexylamine, diethylcyclohexylamine, tetrahydrofuriurylamine, dltetrahydroiuriurylamine, di-beta-alkoxy-ethylamine, morpholine, ethylenediamine, tetramethylammonlum hydroxide, etc.

The compounds of my invention are useful as suriace-active compounds and as such may be employed as wetting agents, emulsifying and disparsing agents, textile assistants, dye-dispersing agents and anti-static as more fully set forth in my above-mentioned U. 8. Patent 2,256,112.

, What I claim is:

1. As new chemical compolmds I Phosphinic acids of ketones having the general Iormula:

OH OH naphthenyl P-i .lnaphthenyl O OH naphthenyl naphthenyl 2. As new chemical compounds phosphinic acids of ketones having the general iormula:

out

on a p-on naphthenyl 3. As new chemical compo nds phosphinic acids of ketones having the general formula:

II naphthenylJZ O OH OH A l div O OH naphthenyl naphthenyl wherein R is a radical composed of carbon and hydrogen selected from thee group of radicals consisting of alkyl, aryl cycloalkyl and naphthenyl. J OSHH E, DXCKETY. 

